TWI694114B - Coloring composition, coloring hardened film, color filter, display element and solid-state imaging element - Google Patents

Abstract

An object of the present invention is to provide a coloring composition that can form a coloring cured film that can achieve good balance and achieve heat resistance, solvent resistance, and developability at a high level.

The coloring composition of the present invention includes (A) a colorant, (B) an adhesive resin, and (C) a polymerizable compound, and the above (A) colorant includes at least one selected from dyes and dye polymers, The dye multimer is provided with a dye monomer having a dye residue and an ethylenically unsaturated group as a structural unit; as (B) an adhesive resin, it contains an ethylenically unsaturated monomer represented by the following formula (1) Of copolymers with a copolymerization ratio of 11 mole% or more (among them, the above-mentioned dye polymers are not included).

In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkanediyl group having 2 to 4 carbon atoms, R ³ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted polycyclic aromatic group Hydrocarbon group, or substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group, n represents an integer of 0-100. However, when n is 2 or more, a plurality of R ² may be the same or different.

Description

Coloring composition, coloring hardened film, color filter, display element and solid-state imaging element

The present invention relates to a coloring composition, a colored hardened film, a color filter, a display element, and a solid-state photographic element. More specifically, it relates to a color liquid crystal display element, a solid-state photographic element, and an organic EL that are formed in a transmissive or reflective type. A coloring composition of a coloring cured film used in display elements, electronic paper, etc., a coloring cured film formed using the coloring composition, a color filter provided with the coloring cured film, a display element, and a solid-state imaging element.

When manufacturing a color filter using a colored radiation-sensitive composition, a method is known in which a pigment-dispersed coloring radiation-sensitive composition is coated on a substrate and dried, and then a desired pattern is applied to the dried coating film The shape is irradiated with radiation (hereinafter referred to as "exposure") and developed, whereby pixels of three primary colors of red, green, and blue are arranged on the substrate (so-called photolithography. For example, refer to Patent Documents 1 and 2). In addition, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, refer to Patent Document 3). In addition, a method of obtaining pigments of each color by an inkjet method using a pigment-dispersed coloring resin composition is also known (for example, refer to Patent Document 4).

In recent years, high-contrast liquid crystal display elements and high-definition solid-state imaging elements have been strongly requested, and in order to achieve these goals, studies using dyes as colorants have been conducted. However, in the case of using a dye as a colorant, the heat resistance of the colored pattern becomes insufficient in most cases compared with the case of using a pigment. Under such a background, as a coloring composition capable of forming a coloring pattern excellent in heat resistance and the like, for example, Patent Document 5 proposes a pigment polymer containing a polymerizable group, a pigment, a polymerizable compound, and a photopolymerization The coloring composition of the initiator serves as a coloring agent.

Prior technical literature Patent Literature

Patent Literature 1 Japanese Patent Laid-Open No. 2-144502

Patent Document 2 Japanese Patent Laid-Open No. 3-53201

Patent Document 3 Japanese Patent Laid-Open No. 6-35188

Patent Document 4 Japanese Patent Laid-Open No. 2000-310706

Patent Literature 5 Japanese Patent Application Publication No. 2013-28764

However, studies by the present inventors have revealed that the coloring pattern formed using the coloring composition described in Patent Document 5 described above has low developability and insufficient heat resistance and solvent resistance.

Therefore, an object of the present invention is to provide a coloring composition that can form a coloring cured film that can achieve good balance and achieve heat resistance, solvent resistance, and developability at a high level. Furthermore, an object of the present invention is to provide a coloring cured film formed using the colored composition, a color filter, a display element, and a solid-state imaging element provided with the colored cured film.

After intensive research, the inventors found that by containing at least one selected from the group consisting of dyes and dye polymers, a polymerizable compound, and a binder resin, the monomer having a specific structure is contained in a specific copolymerization ratio The copolymer can solve the above problems.

That is, the present invention is a coloring composition comprising: (A) a colorant comprising at least one selected from dyes and dye polymers, the dye polymers having dye residues and vinylity Unsaturated group of dye monomer as a structural unit, (B) adhesive resin, and (C) polymerizable compound, as (B) adhesive resin, containing an ethylenically unsaturated monomer represented by the following formula (1) A copolymer having a copolymerization ratio of at least 11 mol% (excluding the above-mentioned dye multimer).

[In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a C2-C4 alkanediyl group, R ³ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted polycyclic aromatic group Group hydrocarbon group, or substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group, n represents an integer of 0-100. However, when n is 2 or more, a plurality of R ² may be the same or different].

In addition, the present invention provides a coloring cured film formed using the above-mentioned colored composition, and a display device provided with the colored cured film. Here, the "colored hardened film" refers to pixels of various colors used for display elements or solid-state imaging elements, protective films, black matrices, spacers, insulating films, and the like.

According to the present invention, even if at least one selected from dyes and dye polymers is used as a colorant, it is possible to form a color-cured film that can achieve heat balance, solvent resistance, and developability at a high level with good balance. Coloring composition. Therefore, the color rendering composition of the present invention is extremely suitable for use as typified by color filters for color decomposition of color liquid crystal display elements, solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper Production of various color filters.

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the coloring composition of the present invention will be described in detail.

-(A)Colorant-

The coloring composition of the present invention contains at least one selected from the group consisting of dyes and dye polymers as (A) colorants, the dye polymers containing dye monomers having dye residues and ethylenically unsaturated groups as Structural units.

First, the dye will be described.

The dye is not particularly limited, and the color and material can be appropriately selected according to the application of the color filter or the like, and one or more types can be used in combination. As the dye used in the present invention, for example, in addition to compounds classified as dyes (Dye) in the color index (C.I.; issued by The Society of Dyers and Colourists), well-known dyes can be used.

系染料、三芳基甲烷系染料、花青系染料、蒽醌系染料、偶氮系染料、二亞甲吡咯系染料、喹酞酮系染料、香豆素系染料、吡唑哢系染料、喹啉系染料、硝基系染料、醌亞胺系染料、酞青系染料等。 As such a dye, in view of the structural surface of the chromophore, for example,

Dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, dimethylenepyrrole dyes, quinophthalone dyes, coumarin dyes, pyrazolidine dyes, quinones Porphyrin dyes, nitro dyes, quinone imine dyes, phthalocyanine dyes, etc.

系染料，例如可使用日本特開2013-053292號公報的第[0010]段中記載的化合物，除此以外，還可使用日本特開2013-100463號公報的實施例中記載的式(A1)~(A6)表示的化合物、日本特開2012-181505號公報的第[0038]~[0043]段和第[0048]~[0050]段、日本特開2013-007032號公報的第[0036]~[0038]段等中記載的化合物。 As

For the dyes, for example, the compounds described in paragraph [0010] of Japanese Patent Laid-Open No. 2013-053292 can be used, and in addition, the formula (A1) described in the examples of Japanese Patent Laid-Open No. 2013-100463 can be used. Compounds represented by ~(A6), paragraphs [0038] to [0043] and [0048] to [0050] of Japanese Patent Laid-Open No. 2012-181505, and paragraphs [0036] of Japanese Patent Laid-Open No. 2013-007032 ~ The compound described in paragraph [0038].

As the triarylmethane-based dye, for example, Japanese Patent Application Publication No. 2001-011336, Japanese Patent Application Publication No. 2003-246935, Japanese Patent Application Publication No. 2008-304766, International Publication No. 2010/123071 pamphlet, Japanese Patent Application Publication 2010 -256598, JP 2011-007847, JP 2011-070172, JP 2011-116803, JP 2011-117995, JP 2011-133844, Japanese Laid-Open 2011-227408 Gazette, International Publication No. 2011/152379 Pamphlet, International Publication No. 2011/162217 Pamphlet, Japanese Patent Laid-Open No. 2012-017425, Japanese Patent Laid-Open No. 2012-037740, International Publication No. 2012/036085 Pamphlet, Japanese Patent JP 2012-073291, International Publication No. 2012/053201 Brochure, JP 2012-083652, JP 2012-088615, JP 2012-098522, JP 2013-057053 The compounds described in the Gazette, US Patent Application Publication No. 2013/0141810, International Publication No. 2013/147099 pamphlet, and the like.

As the cyanine-based dye, for example, the components (A-2) to (A-6) described in the examples of Japanese Patent Laid-Open No. 2009-235392, and [0096] of Japanese Patent Laid-Open No. 2012-212089 can be used. [0108] The compounds described in paragraphs, the compounds described in paragraphs [0054] to [0063] of JP 2012-214718, and the paragraphs [0050] to [0054] in paragraphs of JP 2012-214719. The compounds described in etc.

As the anthraquinone-based dye, for example, the compound described in paragraph [0049] of Japanese Patent Laid-Open No. 2013-053292 can be used, and in addition, Japanese Patent Laid-Open No. 2000-129150 and Japanese Patent Laid-Open No. 2008-015530 can also be used. The compound described in paragraph [0071] of Japanese Patent Publication, the compound described in Japanese Patent Laid-Open No. 2013-210621, and the like.

As the azo-based dye, for example, Japanese Patent Application Publication No. 2003-510398, Japanese Patent Application Publication No. 2005-226022, Japanese Patent Application Publication No. 2007-212639, Japanese Patent Application Publication No. 2010-152160, Japanese Patent Application Publication No. 2010-152160 can be used. Announcement 170073, JP 2011-148993, JP 2011-148994, Japan Pyridone pairs described in Japanese Patent Laid-Open No. 2011-148995, Japanese Patent Laid-Open No. 2012-041461, Japanese Patent Laid-Open No. 2012-062461, International Publication No. 2012/039361 Pamphlet, and Japanese Patent Laid-Open No. 2012-194200 Nitrogen-based dyes; for example, Japanese Patent Application Publication No. 04-249549, Japanese Patent Application Publication No. 2005-120132, Japanese Patent Application Publication No. 2005-298636, Japanese Patent Application Publication No. 2007-197538, Japanese Patent Application Publication No. 2010-275531, Diazo dyes described in Japanese Patent Laid-Open No. 2012-141429, etc.; for example, monoazo dyes described in Japanese Patent Laid-Open No. 2004-325864, Japanese Patent Laid-Open No. 2010-275533, etc.; for example, Japanese Patent Laid-Open No. 2005 -274788, JP 2005-290351, JP 2006-039301, JP 2007-041076, JP 2007-041050, JP 2009-067748, Pyrazole azo dyes described in Japanese Patent Laid-Open No. 2010-170116, Japanese Patent Laid-Open No. 2010-170117, etc.; for example, paragraphs [0058] to [0061] of Japanese Patent Laid-Open No. 2007-293127, Japanese Patent In addition to the methine-based azo dyes described in paragraph [0014] of JP 2011-219655 and JP 2013-145258, etc., other JP 2010-150416, JP JP 2010-152159, JP 2010-170074, JP 2011-016974, JP 2011-074270, JP 2011-145540, US Patent Application Publication No. 2013/ The compound described in the specification of 0164681, etc.

As the methylenepyrrole-based dye, for example, Japanese Patent Laid-Open No. 2008-292970 and Japanese Patent No. 5085256 can be used In addition to the compounds described in, etc., a polymerizable group-containing dimethylenepyrrole compound described in Japanese Patent Laid-Open No. 2011-180306 can be used.

As the quinophthalone-based dye, for example, the formulas described in Japanese Patent Laid-Open No. 5-039269, Japanese Patent Laid-Open No. 6-220339, Japanese Patent Laid-Open No. 8-171201, and Japanese Patent Laid-Open No. 2006-126649 can be used. 2) The compound represented, the compound represented by the formula (1) described in JP 2010-250291, and the compound represented by the formula (1) described in JP 2013-209614.

As the coumarin-based dye, for example, the compound described in Example 4 of Japanese Patent Laid-Open No. 4-179955, the compound represented by the formula (1) described in Japanese Patent Laid-Open No. 2013-151668, and Japanese Patent Laid-Open No. 2013 -The compound represented by the formula (1) described in JP-231165, and the compound represented by the formula (1) described in JP-A-2014-044419.

As the pyrazolone-based dye, for example, a compound represented by formula (1) described in JP 2006-016564 and a compound represented by formula (1) described in JP 2006-063171 can be used.

As the phthalocyanine-based dye, for example, the compounds described in Japanese Patent Laid-Open No. 2004-233504 and Japanese Patent Laid-Open No. 2006-047497 can be used, and in addition to this, the No. [0147] of Japanese Patent Laid-Open No. 2007-094181 can also be used. ] The compounds described in paragraphs [0155], etc.

In addition, as the dye, any one of acid dyes, basic dyes, and nonionic dyes can be suitably used. Here, "acid dye" in this specification is an ionic dye whose anion part becomes a chromophore Means that ionic dyes that form salts with the anion portion also serve as acid dyes. In addition, in this specification, "basic dye" means an ionic dye whose cation portion becomes a chromophore, and an ionic dye that forms a salt with this cation portion also serves as a basic dye. "Non-ionic dye" means dyes other than acid dyes and basic dyes.

系酸性染料、喹啉系酸性染料、硝基系酸性染料、花青系酸性染料等。酸性染料可使用1種或組合2種以上使用，併用2種以上時，也可以任意組合。 Examples of the acid dyes include azo acid dyes, triarylmethane acid dyes, anthraquinone acid dyes,

Acid dyes, quinoline acid dyes, nitro acid dyes, cyanine acid dyes, etc. One type of acid dye may be used alone or two or more types may be used in combination. When two or more types are used in combination, any combination may be used.

Specific examples of the azo acid dye include, for example, CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 59, CI Active Yellow 2, CI Active Red 17, CI Active Red 120, CI Active Black 5, CI Medium Red 7, CI Medium Yellow 5, CI Medium Black 7, CI Direct green 28 and so on.

Specific examples of triarylmethane acid dyes include C.I. Acid Blue 9 and the like.

Specific examples of the anthraquinone-based acid dye include, for example, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Active Blue 19, and C.I. Active Blue 49.

系酸性染料的具體例，例如可舉出C.I.酸性紅52、C.I.酸性紅87、C.I.酸性紅92、C.I.酸性紅289、C.I.酸性紅388，除此以外，可舉出日本特開2010-32999 號公報的合成例1~3、日本特開2011-138094號公報所公開的染料等。 As

Specific examples of the acid dyes include, for example, CI acid red 52, CI acid red 87, CI acid red 92, CI acid red 289, CI acid red 388, and in addition, Japanese Patent Laid-Open No. 2010-32999 Synthesis examples 1 to 3 of the gazette, dyes disclosed in Japanese Patent Laid-Open No. 2011-138094, and the like.

As specific examples of the quinoline-based acid dye, for example, C.I. Acid Yellow 3 and the like can be mentioned.

Specific examples of the nitro acid dye include C.I. acid yellow 1, C.I. acid orange 3, and the like.

Specific examples of the cyanine acid dye include C.I. Reactive Yellow 1 and the like.

系鹼性染料、醌亞胺系鹼性染料、花青系鹼性染料等。鹼性染料可使用1種或組合2種以上使用，併用2種以上時，也可以任意組合。 Examples of the basic dyes include azo-based basic dyes, triarylmethane-based basic dyes,

Basic dyes, quinone imine basic dyes, cyanine basic dyes, etc. The basic dye may be used alone or in combination of two or more, and when two or more are used in combination, any combination may be used.

Specific examples of the azo-based basic dye include, for example, C.I. Basic Blue 41 and C.I. Basic Red 18, and in addition to those described in Japanese Patent Application Laid-Open No. 2011-145540.

As specific examples of triarylmethane-based basic dyes, for example, CI basic blue 7 and CI basic green 1 may be mentioned, and in addition to this, International Publication No. 2010/123071 pamphlet, Japanese Patent Laid-Open No. 2011- The dyes described in 116803, JP 2011-117995, and JP 2011-133844.

系鹼性染料的具體例，例如可舉出C.I.鹼性紫11等。 As

Specific examples of the basic dyes include CI basic violet 11 and the like.

Specific examples of the quinimine-based basic dye include C.I. Basic Blue 3, C.I. Basic Blue 9, and the like.

Specific examples of the cyanine-based basic dye include, for example, CI basic red 12, CI basic red 13, CI basic red 14, CI basic violet 7, CI basic violet 16, CI basic yellow 1 , CI Basic Yellow 11, CI Basic Yellow 13, CI Basic Yellow 21, CI Basic Yellow 28, CI Basic Yellow 51, etc.

In addition, various basic dyes described in Japanese Patent Publication No. 2007-503477 can be mentioned.

Examples of the non-ionic dyes include azo-based non-ionic dyes, anthraquinone-based non-ionic dyes, phthalocyanine-based non-ionic dyes, nitro-based non-ionic dyes, and methine-based non-ionic dyes. Wait. One type of nonionic dye may be used alone or two or more types may be used in combination. When two or more types are used together, any combination may be used.

Specific examples of the azo-based nonionic dyes include, for example, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, and in addition, Japanese Patent Laid-Open No. 2010-170073, Japanese Patent Dye 2010-170074, Japanese Patent Application Publication No. 2010-275531, Japanese Patent Application Publication No. 2010-275533, etc.

Specific examples of the anthraquinone-based nonionic dye include C.I. reduction blue 4, C.I. dispersion red 60, C.I. dispersion blue 56, C.I. dispersion blue 60, and the like.

Specific examples of the phthalocyanine-based nonionic dye include C.I. reduction blue 5 and the like.

Specific examples of the quinoline-based nonionic dye include C.I. Solvent Yellow 33 and C.I. Disperse Yellow 64.

Specific examples of nitro-based nonionic dyes include C.I. Disperse Yellow 42 and the like.

Specific examples of the methine-based nonionic dye include C.I. Solvent Yellow 179 and Disperse Yellow 201.

In addition, various nonionic dyes described in claim 3 or claim 4 of Japanese Patent Application Laid-Open No. 2010-168531 can be mentioned.

系染料、偶氮系染料、次甲基系染料、二亞甲吡咯系染料、花青系染料，更佳為選自三芳基甲烷系染料、

系染料、二亞甲吡咯系染料以及花青系染料中的染料，進一步更佳為選自三芳基甲烷系染料、二亞甲吡咯系染料以及花青系染料中的染料，更進一步更佳為三芳基甲烷系染料。 In the present invention, as dyes, acid dyes and basic dyes are preferred, and from the viewpoint of the structural surface of the chromophore, triarylmethane dyes,

Dyes, azo dyes, methine dyes, dimethylpyrrole dyes, cyanine dyes, more preferably selected from triarylmethane dyes,

The dyes of the series dyes, dimethylenepyrrole-based dyes and cyanine dyes are more preferably dyes selected from triarylmethane-based dyes, dimethylenepyrrole-based dyes and cyanine dyes, even more preferably Triarylmethane dyes.

Next, the dye polymer will be described.

The dye multimer is a polymer having a dye monomer having a dye residue and an ethylenically unsaturated group as a structural unit. The dye polymer can be used alone or in combination of two or more.

系染料、三芳基甲烷系染料、花青系染料、蒽醌系染料、偶氮系染料、二亞甲吡咯系染料、喹酞酮系染料、香豆素系染料、吡唑啉酮系染料、喹啉系染料、硝基系染料、醌亞胺系染料、以及酞青系染料中的染料的殘基。在此，本說明書中「染料殘基」是指，從染料化合物中去除一個氫原子的殘基。其中，作為染料殘基，較佳為選自三芳基甲烷系染料、

系染料、偶氮系染料、二亞甲吡咯系染料、次甲基系染料、以及花青系染 料中的染料的殘基，更佳為選自三芳基甲烷系染料、

系染料、二亞甲吡咯系染料以及花青系染料中的染料的殘基，進一步更佳為三芳基甲烷系染料的殘基。再者，染料殘基可以來自酸性染料、鹼性染料以及非離子性染料中的任一種，但較佳為來自酸性染料、鹼性染料。 As the residue of the dye, in view of the structural surface of the chromophore, for example, selected from

Dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, methylenepyrrole dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, Residues of dyes in quinoline dyes, nitro dyes, quinone imine dyes, and phthalocyanine dyes. Here, "dye residue" in this specification refers to a residue in which one hydrogen atom is removed from the dye compound. Among them, the dye residue is preferably selected from triarylmethane dyes,

Dye residues, azo dyes, dimethylenepyrrole dyes, methine dyes, and cyanine dyes, the residues of the dyes are more preferably selected from triarylmethane dyes,

The residues of the dyes in the series dyes, the dimethylpyrrole series dyes, and the cyanine series dyes are more preferably the residues of triarylmethane series dyes. Furthermore, the dye residue may be derived from any one of acid dyes, basic dyes, and nonionic dyes, but it is preferably derived from acid dyes, basic dyes.

Examples of the ethylenically unsaturated group include vinyl, allyl, and (meth)acryloyl.

As said dye monomer, the monomer represented by following formula (2) is mentioned, for example.

[In formula (2), R ¹¹ represents a hydrogen atom or a methyl group, X ¹ represents a single bond, a substituted or unsubstituted divalent hydrocarbon group, or 1 containing the divalent hydrocarbon group and atoms other than carbon atoms and hydrogen atoms. A divalent group composed of more than one linking group, D ¹ represents a dye residue].

As R ¹¹ , a hydrogen atom or a methyl group can be appropriately selected.

Examples of the divalent hydrocarbon group of X ¹ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. In addition, the "alicyclic hydrocarbon group" in this specification means the concept which does not include the aliphatic hydrocarbon group which does not have a cyclic structure. The divalent aliphatic hydrocarbon group may be in a linear or branched form, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be saturated hydrocarbon groups or unsaturated hydrocarbon groups. In addition, in this specification, "alicyclic hydrocarbon group" and "aromatic hydrocarbon group" mean not only a group consisting of a ring structure but also a group further substituted with a divalent aliphatic hydrocarbon group in the ring structure. Conceptually, it is sufficient that the structure contains at least an alicyclic hydrocarbon or an aromatic hydrocarbon.

Examples of the divalent aliphatic hydrocarbon group include alkanediyl groups and alkenyldiyl groups, and the number of carbon atoms is preferably 1-20, more preferably 2-12, and even more preferably 2-6. Specific examples include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, Propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane -1,4-diyl, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl, 2-methylpropane-1,2-diyl , 2,2-dimethylpropane-1,3-diyl, ethylene-1,1-diyl, ethylene-1,2-diyl, propylene-1,2-diyl, propylene-1,3- Diyl, propylene-2,3-diyl, 1-butene-1,2-diyl, 1-butene-1,3-diyl, 1-butene-1,4-diyl, 2- Pentene-1,5-diyl, 3-hexene-1,6-diyl, etc.

Examples of the divalent alicyclic hydrocarbon group include a cycloalkylene group and a cycloalkenyl group, and the number of carbon atoms is preferably 3-20, and more preferably 3-12. Specific examples include monocyclic hydrocarbon cyclic groups such as cyclopropylene, cyclobutylene, cyclopentylyl, cyclohexyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; 1 , 4-norbornenyl, 2,5-norbornenyl and other norbornenyl; 1,5-adamantylene (1,5-adamantylene), 2,6-adamantyl and other bridged cyclic hydrocarbon groups, etc. .

Examples of the divalent aromatic hydrocarbon group include arylene groups, preferably monocyclic to tricyclic arylene groups having 6 to 14 carbon atoms. As a specific example, For example, phenylene, biphenylene, naphthyl, phenanthrenyl, anthracenyl and the like can be mentioned.

In addition, in the divalent group formed by combining a divalent hydrocarbon group and one or more linking groups containing atoms other than carbon atoms and hydrogen atoms, examples of the linking group include -O- and- S-, -SO ₂ -, -CO-, -COO-, -OCO-, -CONR ^a- (R ^a represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -NR ^a- (R ^a and The above meanings are the same), and may have one kind or two or more kinds. The bonding position of the linking group is arbitrary, and for example, it may be provided between the terminal of the divalent hydrocarbon group or the CC bond, and among them, it is preferably provided between the one-sided terminal or the CC bond. In addition, the divalent hydrocarbon group may be bonded to the above-mentioned linking group to form a ring structure. In addition, the number of carbon atoms mentioned in paragraph [0030] means the total number of carbon atoms excluding the portion of the carbon atoms constituting the linking group.

As specific examples of the divalent hydrocarbon group having the above-mentioned linking group between the CC bonds, for example, -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -, -CH ₂ -CH(- CH ₃ )-CH ₂ -COO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -OCO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -COO- CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -(CH ₂ ) ₅ -COO-(CH ₂ ) ₁₁ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -C-(COO-CH ₂ -CH ₃ ) ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -(CH ₂ -CH ₂ -O) _p -CH ₂ -(p is an integer from 1 to 8), -(CH ₂ -CH ₂ -CH ₂ -O) _q -CH ₂ -(q is an integer from 1 to 5), -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₂ -, -CH ₂ -CH-(OCH ₃ )-, -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CO-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -NH-COO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OCO-CH ₂ -, etc., but not limited to these.

In addition, as specific examples of the group having a ring structure formed by bonding a divalent hydrocarbon group to the above-mentioned linking group, for example, the following groups may be mentioned, but they are not limited thereto.

Examples of the substituent that the divalent hydrocarbon group has include a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, and the like. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The alkoxy group may be in a linear or branched form, and preferably has 1 to 6 carbon atoms. Specific examples include methoxy, ethoxy, propoxy, butoxy and the like. The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include phenoxy group and benzyloxy group. In addition, examples of the substituent of the alkoxy group and the aryloxy group include halogen Element atoms, nitro, hydroxyl, amine, carboxyl, sulfanyl, etc. In addition, when the divalent hydrocarbon group is a divalent alicyclic hydrocarbon group and a divalent aromatic hydrocarbon group, the substituent may have a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. The number of carbon atoms of the alkyl group and the alkenyl group is preferably 1 to 6. Specific examples of the alkyl group include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, hexyl, etc. In addition, as the alkenyl group Specific examples include vinyl, 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, and the like. In addition, as the substituent of the alkyl group and the alkenyl group, the same group as the substituent of the above-mentioned divalent hydrocarbon group may be mentioned.

系染料、三芳基甲烷系染料、花青系染料、蒽醌系染料、偶氮系染料、二亞甲吡咯系染料、喹酞酮系染料、香豆素系染料、吡唑啉酮系染料、喹啉系染料、硝基系染料、醌亞胺系染料、以及酞青系染料中的染料的殘基。其中，作為染料殘基，較佳為選自三芳基甲烷系染料、

系染料、偶氮系染料、二亞甲吡咯系染料、次甲基系染料、以及花青系染料中的染料的殘基，更佳為選自三芳基甲烷系染料、

系染料、二亞甲吡咯系染料以及花青系染料中的染料的殘基，進一步更佳為三芳基甲烷系染料的殘基。再者，染料殘基可以來自酸性染料、鹼性染料以及非離子性染料中的任一種，較佳為來自酸性染料、鹼性染料。 D ¹ represents a dye residue, for example, selected from

Dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, methylenepyrrole dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, Residues of dyes in quinoline dyes, nitro dyes, quinone imine dyes, and phthalocyanine dyes. Among them, the dye residue is preferably selected from triarylmethane dyes,

Dye residues, azo dyes, dimethylenepyrrole dyes, methine dyes, and cyanine dyes, the residues of the dyes are more preferably selected from triarylmethane dyes,

The residues of the dyes in the series dyes, the dimethylpyrrole series dyes, and the cyanine series dyes are more preferably the residues of triarylmethane series dyes. Furthermore, the dye residue may be derived from any of acid dyes, basic dyes, and nonionic dyes, and preferably derived from acid dyes, basic dyes.

The method for synthesizing the dye monomer is not particularly limited, and conventionally known methods can be used. For example, the compound represented by the above formula (2) can be The dye is synthesized by introducing a group having an ethylenically unsaturated group into the basic skeleton of the above-mentioned dye having a functional group by a general organic synthesis method, or after introducing a group having an ethylenically unsaturated group into the synthetic raw material of the dye Got. More specifically, the descriptions of Japanese Patent Laid-Open No. 2013-178478, Japanese Patent Laid-Open No. 2013-173850, Japanese Patent Laid-Open No. 2013-210621, Japanese Patent Laid-Open No. 2013-028764, etc. can be referred to.

Moreover, by polymerizing the dye monomer, a dye multimer can be produced. For the polymerization reaction, a conventionally known method can be used, and for example, the same method as the (B) adhesive resin described later can be used.

The weight average molecular weight (Mw) of polystyrene in the dye polymer of the present invention measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) is usually 1,000 to 100,000, which is It is preferably 3000 to 50000, further preferably 3000 to 30000. By forming such an aspect, heat resistance, solvent resistance, and developability can be achieved at a higher level with good balance.

In addition, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the adhesive resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. In addition, Mn mentioned here means the number average molecular weight converted into polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The dye polymer may be composed of only the dye monomer, but from the viewpoint of achieving a good balance and achieving higher levels of heat resistance, solvent resistance, and developability, it is preferable to have copolymerizable ethylene other than the dye monomer Unsaturated monomer (hereinafter also referred to as "unsaturated monomer (a)") Copolymer as a structural unit. Examples of such unsaturated monomers (a) include monomers represented by the following formula (3), ethylenically unsaturated monomers having at least one carboxyl group, N-substituted maleimide, Aromatic vinyl compounds, vinyl ethers, ethylenically unsaturated monomers having an ethylene oxide or propylene oxide group, macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, etc. . The unsaturated monomer (a) can be used alone or in combination of two or more.

[In formula (3), R ¹² represents a hydrogen atom or a methyl group, R ¹³ represents an alkanediyl group having 2 to 4 carbon atoms, R ¹⁴ represents a substituted or unsubstituted hydrocarbon group, and M represents an integer of 0 to 100. However, when m is 2 or more, a plurality of R ¹³ may be the same or different].

First, the definition of each symbol in equation (3) will be described.

As R ¹² , a hydrogen atom or a methyl group can be appropriately selected.

Examples of the alkanediyl having 2 to 4 carbon atoms in R ¹³ include ethylidene, ethane-1,1-diyl, propane-1,1-diyl, and propane-1,2-di Group, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, etc. Among them, a C2-C3 alkanediyl group is preferred, and ethylidene and propane-1,2-diyl groups are more preferred.

^Examples of the hydrocarbon group in R ¹⁴ include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

The aliphatic hydrocarbon group may be in a linear or branched form, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl and the like. In addition, the alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, and more preferably an alkenyl group having 2 to 12 carbon atoms. Specific examples thereof include a vinyl group, a 1-propenyl group, and a 1-butanyl group. Alkenyl, 1,3-butadienyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4- Vinyl)-5-hexenyl, 2-decenyl and the like. The alkynyl group is preferably an alkynyl group having 2 to 20 carbon atoms, and more preferably an alkynyl group having 2 to 12 carbon atoms. Specific examples include ethynyl, 1-propynyl, and 1-butynyl. Group, 1-pentyne, 3-pentyne, 1-hexyne, 2-ethyl-2-butynyl, 2-octyne, (4-ethynyl)-5-hexyne, 2-decynyl Wait. Among them, the aliphatic hydrocarbon group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 12 carbon atoms.

The alicyclic hydrocarbon group includes a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spiro hydrocarbon group, a cyclic terpene olefin group, and the like. The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 4 to 30 carbon atoms, more preferably an alicyclic hydrocarbon group having 4 to 18 carbon atoms, and even more preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms Hydrocarbyl. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, tertiary butylcyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, decahydro-2-naphthyl, Tricyclo[5.2.1.0 ^2,6 ]decane-8-yl, pentacyclopentadecyl, isobornyl, adamantyl, dicyclopentyl, dicyclopentenyl, tricyclopentyl, Tricyclopentenyl and so on.

The aromatic hydrocarbon group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Here, "aryl" in this specification means a monocyclic to 3-cyclic aromatic hydrocarbon group, and specific examples include phenyl, benzyl, o-tolyl, m-tolyl, p-tolyl, and xylene. Group, naphthyl group, anthracenyl group, phenanthrenyl group, azulenyl group, 9- stilbyl group, etc.

Examples of the substituent of the hydrocarbon group include a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amine group, a substituted or unsubstituted alkoxy group, and the like. When R ¹⁴ is an alicyclic hydrocarbon group or an aromatic hydrocarbon group, the substituent may have a substituted or unsubstituted alkyl group. The alkyl group may be in any form of a straight chain or a branched chain, and the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 4. The alkoxy group may be in any form of a straight chain or a branched chain, and the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 4. In addition, as a specific example of a halogen atom, an alkyl group, and an alkoxy group, the same group as the above-mentioned divalent hydrocarbon group is mentioned. In addition, examples of the substituent of the alkyl group and the alkoxy group include a halogen atom, a hydroxyl group, a nitro group, an amine group, and a cyano group. Furthermore, the position and number of substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different.

Among them, the hydrocarbon group in R ¹⁴ is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and still more preferably an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 10 carbon atoms.

m represents an integer of 0 to 100, but m may be 0 or may not have an R ¹³ O group. In the case of having an R ¹³ O group, m is preferably an integer of 1 to 30, more preferably an integer of 1 to 15, even more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 5. When m is 2 or more, a plurality of R ¹³ groups may be the same or different, and a plurality of R ¹³ O groups may be bonded in any order. As an example in which a plurality of R ^{13 are} different, for example, a combination of a C2 alkanediyl group and a C3 alkanediyl group; a C2 alkanediyl group and a C2 number A combination of an alkanediyl group of 3 and a C4 alkanediyl group. Among them, the combination of ethylidene and propane-1,2-diyl, the combination of ethylidene and propane-1,3-diyl, the ethylidene and propane-1,2-diyl and butane are preferred -1,4-diyl combination, ethylidene and propane-1,3-diyl and butane-1,4-diyl combination.

Specific examples of the monomer represented by the following formula (3) include methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (meth) (Meth) acrylic acid alkyl esters such as 2-hydroxyethyl acrylate; vinyl (meth) acrylate, allyl (meth) acrylate and other (meth) acrylate; benzene (meth) acrylate Ester, aryl (meth)acrylate such as benzyl (meth)acrylate; polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (Meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, glycerol mono (meth) acrylic (Meth)acrylates of polyols such as esters; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo (meth)acrylate [5.2.1.0 ^2,6 ]decane- (Meth)acrylates such as 8-yl esters, dicyclopentenyl (meth)acrylates, etc. having alicyclic hydrocarbon groups.

Examples of the ethylenically unsaturated monomer having one or more carboxyl groups include (meth)acrylic acid, maleic acid, maleic anhydride, and succinic acid mono[2-(meth)acryloyloxyethyl]ester , Ω-carboxy polycaprolactone mono (meth) acrylate, vinyl p-benzoate, etc.

Examples of N-substituted maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, acenaphthylene and the like.

Examples of vinyl ethers include cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, and pentacyclopentadecyl vinyl ether. Wait.

Examples of the ethylenically unsaturated monomer having an epoxyethyl group include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and β-ethyl (meth)acrylate. Glycidyl ester, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,3,4-ginseng (glycidyloxymethyl) styrene and other ethylenically unsaturated monomers with glycidyl ether groups; 1,2-epoxy-4-vinylcyclohexane; 3,4-epoxycyclohexylmethyl (meth)acrylate, etc.

Examples of the ethylenically unsaturated monomer having a propylene oxide group include 3-(vinyloxymethyl)-2-methylepoxypropane and 2-(vinyloxyethyl)-2- (Vinyloxyalkyl) alkyl propylene oxide such as methyl propylene oxide; 3-[(meth)acryloyloxymethyl] propylene oxide, 2-[2-(meth)acrylonitrile (Ethoxyethyl) propylene oxide (meth)acryloyloxyalkylpropylene oxide; 3-[(meth)acryloyloxymethyl]-2-methylpropylene oxide, 2- [(Meth)acryloyloxyalkyl]alkyl propylene oxide such as [2-(meth)acryloyloxyethyl]-2-ethylpropylene oxide; 2-[(methyl) [(Meth)acryloyloxyalkyl]phenyl propylene oxide such as propylene oxymethyl]-2-phenylpropylene oxide; 4-[3-(3-ethyloxypropylene- 3-ylmethoxy)propoxy]styrene, 4-[7-(3-ethylepoxypropane-3-ylmethoxy)heptoxy]styrene and the like with propylene oxide Aromatic vinyl compounds, etc.

Examples of macromolecular monomers include polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, polysiloxane, and the like. Meth) acryl-based macromonomer.

Among them, the unsaturated monomer (a) preferably contains the monomer represented by the above formula (3).

When the dye multimer is a copolymer of a dye monomer and an unsaturated monomer (a), the copolymerization ratio of the dye monomer in the dye multimer It is preferably 5 to 30 mol%, more preferably 10 to 25 mol%, and still more preferably 10 to 20 mol%.

The copolymerization ratio of the monomer represented by the above formula (3) in the dye multimer is preferably 30 to 85 mol%, more preferably 40 to 80 mol%, and still more preferably 50 to 75 mol%. In this case, when the aryl (meth)acrylate is contained as the monomer represented by the above formula (3), the copolymerization ratio of the aryl (meth)acrylate in the dye polymer is preferably 5 mol% or more and less than 20 mol%, more preferably 7 to 18 mol%, further preferably 10 to 16 mol%.

The coloring composition of the present invention may contain coloring agents other than dyes and dye polymers. Examples of such other colorants include pigments. These other colorants can be used alone or in combination of two or more.

Examples of the pigment include compounds classified as pigments in the color index (C.I.; issued by The Society of Dyers and Colourists), that is, compounds labeled with the following color index (C.I.) numbers.

CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264 and other red pigments; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green pigments such as green 59; CI pigment blue 15: 6, CI pigment blue 16, CI pigment blue 80 and other blue pigments; CI Pigment Yellow 83, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215 and other yellow pigments; CI Pigment Orange 38 and other orange pigments ; CI Pigment Violet 23 and other purple pigments.

In addition to this, the brominated diketopyrrolopyrrole pigment represented by formula (Ic) in Japanese Patent Application Publication No. 2011-523433 can also be used as the red pigment. In addition, Japanese Patent Application Publication No. 2001-081348, Japanese Patent Application Publication No. 2010-026334, Japanese Patent Application Publication No. 2010-191304, Japanese Patent Application Publication No. 2010-237384, Japanese Patent Application Publication No. 2010-237569, Lake pigments described in Japanese Patent Laid-Open No. 2011-006602, Japanese Patent Laid-Open No. 2011-145346, and the like.

In the present invention, when a pigment is contained as the (A) colorant, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. In addition, the pigment can be used after modifying the surface of its particles with a resin as needed. Examples of the resin that modifies the surface of the pigment particles include the carrier resin described in Japanese Patent Laid-Open No. 2001-108817, or various commercially available pigment dispersion resins. As a method of coating the resin on the surface of the carbon black, for example, the methods described in Japanese Patent Laid-Open No. 9-71733, Japanese Patent Laid-Open No. 9-95625, Japanese Patent Laid-Open No. 9-124969, and the like can be used. In addition, organic pigments can be used by so-called salt milling to refine primary particles. As a method of salt milling, for example, the method disclosed in Japanese Patent Laid-Open No. 08-179111 can be used.

In addition, in the present invention, when a pigment is contained as the (A) colorant, it may further contain at least one selected from known dispersants and dispersion aids.

Examples of known dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, and polyoxyethylene alkyl phenyl ether-based dispersants. , Polyethylene glycol diester-based dispersant, sorbitan fatty acid ester-based dispersant, polyester-based dispersant, (meth)acrylic-based dispersant, etc., as commercial products, for example, Disperbyk-2000, Disperbyk -(Meth)acrylic dispersants such as 2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, manufactured by BYK-Chemie (BYK)), Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk -167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK-Chemie (BYK) Co., Ltd.), carbamate-based dispersants such as Solsperse 76500 (manufactured by Lubrizol Corporation), Solsperse 24000 (Lubrizol Corporation) Polyethyleneimine-based dispersants such as ), polyester-based dispersants such as AJISPER PB821, AJISPER PB822, AJISPER PB880, AJISPER PB881 (above, manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc. In addition, BYK- LPN21324 (manufactured by BYK-Chemie (BYK)).

In the present invention, one dispersant can be used alone or in combination of two or more.

In the present invention, the content of the dispersant is preferably 5 to 300 parts by mass relative to 100 parts by mass of the pigment, more preferably 10 to 200 parts by mass, still more preferably 20 to 100 parts by mass, still more preferably 20 to 50 parts by mass.

In addition, examples of the above-mentioned dispersion aid include pigment derivatives. Specific examples of pigment derivatives include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

From the viewpoint of achieving good balance and achieving high levels of heat resistance, solvent resistance, and developability, (A) the content of the colorant in the solid content of the coloring composition is usually 5 to 70% by mass, preferably 5 to 60% by mass, preferably 10-50% by mass, further preferably 15-40% by mass. Here, the solid content is a component other than the solvent described later.

The coloring composition of the present invention may contain the dye and the dye multimer alone as the (A) colorant, but in the case of containing both the dye and the pigment as the (A) colorant, from the viewpoint of being able to more enjoy the effects of the present invention The total content of the dye and the dye polymer is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more with respect to the total colorant. Furthermore, the coloring composition of the present invention can achieve good balance and achieve high levels of heat resistance, solvent resistance, and heat resistance even when the content ratio of the dye and the dye polymer to the solid content of the colored composition is high. It has developability and can form a colored hardened film that suppresses the generation of precipitates and foreign matter in the coating film. In addition, when the dye contains triarylmethane dye, as long as it contains a combination of triarylmethane dye and other blue colorants, or the total content of the dye, triarylmethane dye is 55% by mass or more, you can enjoy more The effect of the present invention.

-(B) Adhesive resin-

The coloring composition of the present invention contains a specific copolymer as (B) an adhesive resin, that is, one containing an ethylenically unsaturated monomer represented by the following formula (1) A copolymer having a copolymerization ratio of 11 mol% or more (hereinafter, also referred to as "specific copolymer". Among them, the above-mentioned dye polymer is not included).

[In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a C2-C4 alkanediyl group, R ³ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted polycyclic aromatic group Group hydrocarbon group, or substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group, n represents an integer of 0-100. However, when n is 2 or more, a plurality of R ¹² may be the same or different].

As R ¹ , a hydrogen atom or a methyl group can be appropriately selected.

Carbon atoms in the alkanediyl group ² R 2 to 4, and in R ¹³ include the groups exemplified the same groups. Among them, an alkanediyl group having 2 to 3 carbon atoms is preferred, and ethylidene and propane-1,2-diyl are more preferred.

Examples of the polycyclic aromatic hydrocarbon group in R ³ include polynuclear aromatic hydrocarbon groups and condensed aromatic hydrocarbon groups. Here, the "polynuclear aromatic hydrocarbon group" in this specification means that there are two or more aromatic rings composed of carbon and hydrogen and the aromatic rings are bonded to each other by a carbon-carbon bond, not only the aromatic rings are The single-bonded hydrocarbon group and the hydrocarbon group formed by bonding with alkanediyl are also included in the "polynuclear aromatic hydrocarbon group". In addition, "condensed aromatic hydrocarbon group" refers to a hydrocarbon group in which two or more aromatic rings composed of carbon and hydrogen exist, and these aromatic rings share one or more adjacent and bonded carbon atoms.

The number of aromatic rings constituting the polycyclic aromatic hydrocarbon group is preferably from 2 to 10, more preferably from 2 to 7, and even more preferably from 2 to 5.

Specific examples of the polynuclear aromatic hydrocarbon group include, for example, biphenyl, bitriphenyl, bitetraphenyl, bipentaphenyl, bihexaphenyl, biheptaphenyl, bioctaphenyl, and binonylbenzene Group, bidecylphenyl, benzylphenyl, phenethylphenyl, etc. Among them, biphenyl and benzylphenyl are preferred.

Specific examples of the condensed aromatic hydrocarbon group include naphthyl, anthracenyl, pyrenyl, phenanthrenyl, perylene, stilbene and the like. Among them, naphthyl, anthracenyl and fluorenyl are preferred, and naphthyl is more preferred.

The nitrogen-containing alicyclic heterocyclic group in R ³ may be a monocyclic type or a polycyclic type. Among them, a monocyclic type is preferred, and a 5-7 member ring is more preferred.

啉基、硫代

啉基、哌啶基、N-六氫吡啶基、哌

基、升哌

基等。其中，較佳為哌啶基。 Specific examples of the nitrogen-containing alicyclic heterocyclic group include, for example, pyrrolidinyl, imidazolidinyl, pyrazolidinyl,

Porphyrinyl, thio

Porphyrinyl, piperidinyl, N-hexahydropyridyl, piper

Base

Base etc. Among them, piperidinyl is preferred.

Examples of the substituent of the phenyl group, polycyclic aromatic hydrocarbon group, and nitrogen-containing alicyclic heterocyclic group include halogen atoms, hydroxyl groups, nitro groups, amine groups, cyano groups, substituted or unsubstituted alkyl groups, substituted or Unsubstituted alkoxy, etc. The alkyl group may be in a linear or branched form, and the number of carbon atoms is preferably 1-20, more preferably 1-15, and even more preferably 1-10. In addition, the alkoxy group may be in a linear or branched form, and the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. As Specific examples of the halogen atom, alkyl group, and alkoxy group include the same groups as those exemplified above. In addition, examples of the substituent of the alkyl group and the alkoxy group include a halogen atom, a hydroxyl group, a nitro group, an amine group, and a cyano group. Furthermore, the position and number of substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different.

In addition, when the substituent of the phenyl group and the polycyclic aromatic hydrocarbon group is a hydroxyl group, the hydroxyl group may be protected. Examples of the protecting group for a hydroxyl group include an ether protecting group, an acetal protecting group, an acyl group protecting group, an alkoxycarbonyl group, and a silane ether protecting group, which can be appropriately selected. Examples of the ether protecting group include methyl, benzyl, methoxybenzyl, and tertiary butyl, and examples of the protecting group include acetyl acetyl, trimethyl acetyl, phenyl acetyl, and the like. As the alkoxycarbonyl group, for example, ethoxycarbonyl group, phenoxycarbonyl group, tertiary butyloxycarbonyl group and the like are mentioned, and as the silane ether protecting group, trimethylsilyl group and tertiary butyl group are mentioned. Based on dimethyl silane. In addition, examples of the acetal protecting group include methoxymethyl, ethoxyethyl, tetrahydropyranyl, and tetrahydrofuran. Among them, from the viewpoint of heat resistance, solvent resistance, and developability, the protective group for the hydroxyl group is preferably an acetal protective group. In addition, the method of introducing a protective group into a hydroxyl group can use a well-known method.

Among them, R ^{3 is} preferably substituted or unsubstituted phenyl, substituted or unsubstituted polynuclear aromatic hydrocarbon group, substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group, more preferably substituted or unsubstituted Phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted piperidinyl, further preferably phenyl which may be substituted by hydroxy, biphenyl which may be substituted by hydroxy, and hydroxy and alkyl Benzylphenyl, substituted piperidinyl. Furthermore, the hydroxyl group may be protected by a protecting group.

n represents an integer of 1 to 100, but n may be 0 or may not have an R ² O group. In the case of having an R ² O group, n is preferably an integer of 1 to 30, more preferably an integer of 1 to 15, even more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 5. When n is 2 or more, a plurality of R ² may be the same or different, and a plurality of R ² O groups may be bonded in any order. Among them, n is preferably 0 from the viewpoint of achieving a good balance and achieving heat resistance, solvent resistance, and developability at a higher level.

(B) The adhesive resin may be composed of only the ethylenically unsaturated monomer represented by formula (1), but from the viewpoint of developability, it is preferably formed to have a structure other than the ethylenically unsaturated monomer represented by formula (1). Other copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as "unsaturated monomer (b)") is a copolymer of structural units. Examples of such unsaturated monomers (b) include alkyl (meth)acrylates, alkenyl (meth)acrylates, (meth)acrylates of polyols, and (alicyclic hydrocarbon groups) ( Methacrylates, ethylenically unsaturated monomers with more than one carboxyl group, N-substituted maleimide, aromatic vinyl compounds, vinyl ethers, ethylene with epoxyethyl or propylene oxide groups Unsaturated monomers, macromonomers having a single (meth)acryloyl group at the end of the polymer molecular chain, etc. Specific examples of these monomers include the same monomers as those exemplified in the unsaturated monomer (a). The unsaturated monomer (b) can be used alone or in combination of two or more.

Among them, the unsaturated monomer (b) is preferably an ethylenically unsaturated monomer having one or more carboxyl groups from the viewpoint of developability.

As the other monomer, it is preferable to contain one or more kinds selected from alkyl (meth)acrylate, N-substituted maleimide and aromatic vinyl compound.

(B) The copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) in the adhesive resin is 11 mol% or more in the entire structural unit, but from the viewpoint of further improving heat resistance and solvent resistance, It is preferably 14 mol% or more, more preferably 18 mol% or more, and still more preferably 22 mol% or more. From the viewpoint of further improving developability and ease of synthesis, it is preferably 60 mol% % Or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less. As the range of the copolymerization ratio, it is preferably from 11 to 60 mol%, more preferably from 14 to 60 mol%, even more preferably from 18 to 50 mol%, even more preferably from 22 to 50 mol%, and more It is even better to be 22-40 mole %. Furthermore, when R ³ of the ethylenically unsaturated monomer represented by formula (1) is a hydroxy substituted phenyl group or a hydroxy substituted polycyclic aromatic hydrocarbon group and the hydroxy group is protected by an acetal protecting group, (B) an adhesive The copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) in the resin may not necessarily be 11 mol% or more in the entire structural unit, and the effects of the present invention can be exerted, and is particularly effective for improving heat resistance.

(B) The copolymerization ratio of the ethylenically unsaturated monomer having one or more carboxyl groups in the adhesive resin is preferably 10 to 50 mol%, and more preferably 15 to 35 mol% in the entire structural unit.

The adhesive resin in the present invention can be produced by a known method, but for example, methods disclosed in Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. 2006-259680, International Publication No. 2007/029871 pamphlet, etc. can also be used , Control its structure, Mw, Mw/Mn.

The weight average molecular weight (Mw) converted into polystyrene measured by GPC (elution solvent: tetrahydrofuran) of the adhesive resin in the present invention is usually 1,000 to 100,000, preferably 3,000 to 50,000, and more preferably 5,000 to 30,000 . By adopting such an aspect, heat resistance, solvent resistance, and developability can be achieved at a high level with good balance, and the generation of dry foreign matter during coating can be suppressed to a high level.

In addition, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the adhesive resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. In addition, Mn mentioned here means the number average molecular weight converted into polystyrene measured by GPC (elution solvent: tetrahydrofuran).

The coloring composition of the present invention may contain an adhesive resin other than the above-mentioned specific copolymer as the (B) adhesive resin. As such another adhesive resin, a (co)polymer of an unsaturated monomer (b) is preferable, and an unsaturated monomer (b) containing an ethylenically unsaturated monomer having one or more carboxyl groups is more preferable. Of copolymers.

In the present invention, (B) the binder resin can be used alone or in combination of two or more.

(B) The content of the binder resin is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass relative to (A) 100 parts by mass of the colorant. By adopting such an aspect, heat resistance, solvent resistance, and developability can be achieved at a higher level with good balance.

-(C) Polymerizable compound-

In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. As the polymerizable group, for example, B Ethylene unsaturated group, ethylene oxide, propylene oxide group, N-alkoxymethylamine group, etc. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamine groups.

Specific examples of the compound having two or more (meth)acryloyl groups include a polyfunctional (meth)acrylate and caprolactone obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. Modified polyfunctional (meth) acrylate, alkylene oxide modified polyfunctional (meth) acrylate, hydroxyl-containing (meth) acrylate and polyfunctional isocyanate obtained by reaction of polyfunctional amino acid An ester (meth)acrylate, a polyfunctional (meth)acrylate having a carboxyl group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride, and the like.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Such aliphatic polyhydroxy compounds of more than 3 valence. Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol. Penta(meth)acrylate, glycerol dimethacrylate, etc. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride. Diacid anhydride, pyromellic anhydride, and Tetracarboxylic acid dianhydride such as phenyltetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.

In addition, examples of the polyfunctional (meth)acrylate modified with caprolactone include compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. Examples of the polyfunctional (meth)acrylate modified with alkylene oxide include bisphenol A di(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide. 、Isocyanuric acid tri(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, using at least one selected from ethylene oxide and propylene oxide Modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, Pentaerythritol tetra(meth)acrylate modified by at least one of ethylene oxide and propylene oxide, and dipentaerythritol pentaerythritol (methyl) modified by at least one selected from ethylene oxide and propylene oxide Group) acrylate, dipentaerythritol hexa(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, and the like.

環或苯基取代三

環作為基本骨架的化學結構，並且也包含三聚氰胺、苯并胍胺或它們的縮合物的概念。作為具有2個以上的N-烷氧基甲基胺基的化合物的具體例，可舉出N,N,N’,N’,N”,N”-六(烷氧基甲基)三聚氰胺、N,N,N’,N’-四(烷氧基甲基)苯并胍胺、N,N,N’,N’-四(烷氧基甲基)甘脲等。 In addition, examples of the compound having two or more N-alkoxymethylamine groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. Furthermore, the melamine structure and benzoguanamine structure refer to having more than one three

Ring or phenyl substituted three

The ring is the chemical structure of the basic skeleton, and also includes the concept of melamine, benzoguanamine, or their condensates. Specific examples of the compound having two or more N-alkoxymethylamine groups include N,N,N',N',N”,N”-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine, N,N,N',N'-tetra(alkoxymethyl) glycoluril, etc.

Among these polymerizable compounds, polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid and caprolactone-modified polyfunctional (meth) ) Acrylate, polyfunctional urethane (meth)acrylate, polyfunctional (meth)acrylate with carboxyl group, N,N,N',N',N”,N”-hexa(alkoxy) Methyl) melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine. A polyfunctional (methyl) compound obtained by reacting an aliphatic polyhydroxy compound with a trivalent value or more with (meth)acrylic acid from the viewpoint of achieving good balance and achieving higher levels of heat resistance, solvent resistance, and developability Among the acrylates, particularly preferred are trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. Among polyfunctional (meth)acrylates having a carboxyl group, the most preferred are A compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride.

In the present invention, (C) a polymerizable compound can be used alone or in combination of two or more.

(C) The content of the polymerizable compound is preferably 10 to 1000 parts by mass, more preferably 15 to 500 parts by mass, and even more preferably 20 to 150 parts by mass relative to (A) 100 parts by mass of the colorant. By adopting such an aspect, heat resistance, solvent resistance, and developability can be achieved at a higher level with good balance.

-(D) Photopolymerization initiator-

The coloring composition of the present invention may contain a photopolymerization initiator. This makes it possible to impart radiation sensitivity to the colored composition. The photopolymerization initiator used in the present invention utilizes visible light, ultraviolet light, far ultraviolet light Exposure to radiation such as rays, electron beams, X-rays, etc., generates active species of compounds that can initiate polymerization of the polymerizable compound.

化合物、O-醯基肟化合物、鎓鹽化合物、苯偶姻化合物、二苯甲酮化合物、α-二酮化合物、多核醌化合物、重氮化合物、醯亞胺磺酸酯化合物等。 Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, and

Compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, amide imine sulfonate compounds, etc.

化合物、O-醯基肟化合物中的至少1種。 In the present invention, one type of photopolymerization initiator may be used alone or two or more types may be used in combination. As the photopolymerization initiator, it is preferably selected from thioxanthone compounds, acetophenone compounds, biimidazole compounds,

At least one of a compound and an O-acyl oxime compound.

Among the preferred photopolymerization initiators of the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone etc.

啉代丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-

啉代苯基)丁烷-1-酮、2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-

啉代苯基)丁烷-1-酮等。 In addition, specific examples of the acetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2-

Porphyrin-1-one, 2-benzyl-2-dimethylamino-1-(4-

Porinophenyl)butane-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-

Phenylphenyl) butane-1-one and so on.

In addition, specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2 ,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6 -Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc.

唑等硫醇氫供體，4,4'-雙(二甲基胺基)二苯甲酮、4,4'-雙(二乙基胺基)二苯甲酮等胺氫供體。本發明中，氫供體可以使用1種或混合2種以上使用，但從可進一步改進靈敏度的方面考慮，較佳為組合1種以上的硫醇氫供體與1種以上的胺氫供體使用。 In addition, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The "hydrogen donor" as used herein refers to a compound that can supply a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of hydrogen donors include 2-mercaptobenzothiazole and 2-mercaptobenzothiazole.

Thiol and other thiol hydrogen donors, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and other amine hydrogen donors. In the present invention, one kind of hydrogen donor may be used or two or more kinds may be used in combination, but from the viewpoint of further improving sensitivity, it is preferable to combine one or more kinds of thiol hydrogen donors and one or more kinds of amine hydrogen donors use.

化合物的具體例，可舉出2,4,6-參(三氯甲基)-均三

、2-甲基-4,6-雙(三氯甲基)-均三

、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三

、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三

、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-均三

、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-均三

、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-均三

、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-均三

、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-均三

等具有鹵甲基的三

化合物。 In addition, as three

Specific examples of the compound include 2,4,6-ginseng (trichloromethyl)-mesan

, 2-methyl-4,6-bis(trichloromethyl)-all three

, 2-[2-(5-Methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three

、2-[2-(Furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three

、2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all three

, 2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-mesan

, 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-all three

, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-mesan

, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-mesan

Three with halomethyl

Compound.

In addition, specific examples of the O-acyl oxime compound include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-phenyl acetyl oxime), 1-[9-ethyl-6-(2-methylphenacyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyl oxime), 1-[9-ethyl Yl-6-(2-methyl-4-tetrahydrofuran methoxyphenyl acetyl phenyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyl oxime), 1-[9- Ethyl -6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxyphenacyl}-9H-carbazol-3-yl]-ethyl Ketone-1-(O-acetyl oxime), etc. As a commercially available product of the O-acyl oxime compound, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), OXE-03, OXE-04 (above, manufactured by BASF Corporation), and the like can also be used.

In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-bis Ethylaminoacetophenone, 4-dimethylaminobenzeneacetone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5- Bis(4-diethylaminobenzyl)cyclohexanone, 7-diethylamino-3-(4-diethylaminophenyl benzoyl) coumarin, 4-(diethylamino ) Chaketone etc.

In the present invention, the content of (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, and even more preferably 5 to 50 parts relative to (C) 100 parts by mass of the polymerizable compound. Quality parts. By adopting such an aspect, heat resistance can be achieved at a higher level with good balance. Solvent resistance and developability, therefore, can further improve curability and coating characteristics.

-(E) Solvent-

The coloring composition of the present invention is a coloring composition containing the above-mentioned components (A) to (C) and optionally added other components. Usually, a liquid composition is prepared by blending an organic solvent.

As the (E) solvent, as long as the components (A) to (C) and other components constituting the coloring composition are dispersed or dissolved, and do not react with these components, and have moderate volatility, they can be appropriately selected for use.

Examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol Ethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono (Poly)alkanes such as n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Glycol monoalkyl ethers; alkyl lactate such as methyl lactate and ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethyl (Cyclic) alkyl alcohols such as hexanol and cyclohexanol; ketone alcohols such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate , Diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl acetate- (Poly)alkanediol monoalkyl ether acetate such as 3-methoxybutyl ester; glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether; tetrahydrofuran And other cyclic ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexane Diacetate such as glycol diacetate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl Alkoxycarboxylic acid esters such as ethyl-3-methoxybutyl propionate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, acetic acid Isoamyl ester, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, ethyl Fatty acid alkyl esters such as methyl acetate, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-di Acetylamine such as methylacetamide and N-methylpyrrolidone, or internal amide etc.

Among these organic solvents, one or two selected from (poly)alkanediol monoalkyl ether acetate, ketol, and ketone are preferred from the viewpoints of solubility, pigment dispersibility, coatability, and the like. the above.

In the present invention, one type of solvent may be used alone or two or more types may be used in combination.

(E) The content of the solvent is not particularly limited, and the total concentration of each component of the coloring composition other than the solvent is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. By adopting such an aspect, dispersibility and stability can be improved. Therefore, heat resistance, solvent resistance, and developability can be achieved at a higher level with a good balance.

-additive-

The coloring composition of the present invention may contain various additives as needed.

Examples of the additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicone-based surfactants; ; Vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethyl Oxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethyl Adhesion accelerators such as oxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thioxo Bis(4-methyl-6-tertiary butylphenol), 2,6-ditertiary butylphenol, pentaerythritol [3-(3,5-ditertiarybutyl-4-hydroxyphenyl)propane Acid ester], 3,9-bis[2-[3-(3-tertiarybutyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl ]-2,4,8,10-Tetraoxy-spiro[5.5]undecane, thiodiethylidene bis[3-(3,5-ditertiarybutyl-4-hydroxyphenyl)propionic acid Ester] and other antioxidants; 2-(3-tertiary butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxybenzophenones and other ultraviolet absorbers; poly Anti-agglomerating agents such as sodium acrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5- Amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and other residue improvers; succinic acid mono [2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl] ester, ω-carboxy polycaprolactone mono(meth)acrylic acid Developers such as esters, etc.

Method for manufacturing colored composition

The coloring composition of the present invention can be prepared as follows: For example, a dye solution obtained by dissolving at least one selected from dyes and dye polymers as (A) colorants in (E) solvent, (B ) Adhesive resin, (C) polymerizable compound, and additional (E) solvent, and other components are mixed and prepared. In addition, when the coloring composition of the present invention further contains a pigment as the (A) colorant, it can be prepared as follows: in (E) solvent, in the presence of a dispersing agent, the pigment and (B) the binder resin according to the situation A part of it is mixed and dispersed while being pulverized using, for example, a bead mill, roller mill, etc. to form a pigment dispersion liquid, and then, the pigment dispersion liquid is added to dissolve in (E) solvent and (A) is selected from dyes Dye solution obtained with at least one of the dye polymers, (C) polymerizable compound, (B) adhesive resin, (D) photopolymerization initiator as needed, and additional (E) solvent, other Ingredients and mix to prepare. In addition, it can also be prepared as follows: in a solvent (E), in the presence of a dispersant, a pigment is mixed with (A) at least one selected from the group consisting of dyes and dye polymers, dispersed to form a dispersion liquid, and , Add (C) polymerizable compound, (B) adhesive resin, (D) photopolymerization initiator as needed, and additional (E) solvent and other components to this colorant dispersion, and mix to prepare .

Colored hardened film and its forming method

The coloring cured film of the present invention is formed using the coloring composition of the present invention, which contains (A) a coloring agent containing at least one kind selected from dyes and dye polymers, (B) represented by the above formula (1) A copolymer having an ethylenically unsaturated monomer with a copolymerization ratio of 11 mol% or more (which does not include the above-mentioned dye multimer), the above dye multimer is provided with a dye residue and an ethylenic monomer The dye monomer of the saturated group serves as a structural unit. Specifically, it means that each color pixel, black matrix, black spacer, etc. that can be used for the color filter.

Hereinafter, a coloring cured film that can be used for a color filter and a method of forming the same will be described.

As a method of forming a color-cured film constituting a color filter, first, the following method may be mentioned. First, on the surface of the substrate, a light-shielding layer (black matrix) is formed in such a manner as to divide a portion where pixels are formed. Next, on this substrate, after applying a liquid composition of the radiation-sensitive coloring composition of the present invention, for example, red, pre-baking is performed to evaporate the solvent to form a coating film. Next, after exposing this coating film through a photomask, it develops using an alkaline developing solution, and the unexposed part of the coating film is dissolved and removed. Then, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed by post-baking.

Next, using each radiation-sensitive coloring composition of green or blue, coating, pre-baking, exposure, development, and post-baking of each radiation-sensitive coloring composition are performed in the same manner as described above to sequentially form green on the same substrate Pixel array and blue pixel array. As a result, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above order.

In addition, the black matrix can be formed by forming a metal thin film of chromium or the like formed by sputtering or vapor deposition into a desired pattern by photolithography, or a radiation-sensitive coloring composition in which black pigment is dispersed can be used, and The above-described case of forming pixels is similarly formed.

Examples of the substrate used when forming the color-cured film include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide imide, polyimide, and the like.

In addition, these substrates may be subjected to appropriate pretreatments such as reagent treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum evaporation, etc., as necessary.

When coating the radiation-sensitive coloring composition on the substrate, a spray method, a roll coating method, a spin coat method (spin coat method), a slit die coating method (slit coating method), a bar coating method, etc. can be suitably used. The coating method is particularly preferably a spin coating method or a slit die coating method.

The heating and drying conditions in the pre-baking are usually about 1 to 10 minutes at 70 to 110°C.

The coating thickness when forming the cured film of the color filter used in the display element is generally 0.6 to 8 μm, preferably 1.2 to 5 μm, based on the film thickness after drying. In addition, the coating thickness when forming the cured film of the color filter used in the solid-state imaging element is generally 0.3 to 5 μm, preferably 0.5 to 2 μm in terms of the film thickness after drying.

As a light source used to form at least one selected from the pixel and the black matrix, for example, a xenon lamp, halogen lamp, tungsten lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, medium voltage Lamp light sources such as mercury lamps and low-pressure mercury lamps or laser light sources such as argon ion laser, YAG laser, XeCl excimer laser and nitrogen laser. As a light source for exposure, an ultraviolet LED can also be used. Radiation with a wavelength in the range of 190 to 450 nm is preferred.

The exposure amount of radiation is generally preferably 10 to 10000 J/m ² .

In addition, as the alkaline developer, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4 .0] Aqueous solutions of 7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene and the like.

To the alkaline developer, water-soluble organic solvents such as methanol and ethanol, surfactants, etc. may be added in appropriate amounts. Furthermore, after alkaline development, it is usually washed with water.

As the development treatment method, a shower development method, a spray development method, a dip (dip) development method, a dip (liquid bath) development method, or the like can be used. The developing conditions are preferably 5 to 300 seconds at normal temperature.

The post-baking conditions are usually about 180 to 280°C for about 10 to 60 minutes.

When forming a coloring cured film of a color filter used in a display device, the film thickness of the pixel thus formed is 0.5 to 8 μm, preferably 1 to 4 μm. In addition, when forming the coloring cured film of the color filter used in the solid-state imaging element, it is usually 0.3 to 4 μm, preferably 0.5 to 2 μm.

In addition, as the second method of forming the color-cured film constituting the color filter, it is possible to use the inkjet method disclosed in Japanese Patent Laid-Open No. 7-318723, Japanese Patent Laid-Open No. 2000-310706, etc. to obtain pixels of various colors. Methods. In this method, first, a partition having a light-shielding function is formed on the surface of the substrate. Next, after the liquid composition of the thermosetting coloring composition of the present invention, for example, red is ejected into the formed partition wall by an inkjet device, pre-baking is performed to evaporate the solvent. Then, after exposing this coating film as needed, it is hardened by post-baking to form a red pixel pattern.

Next, using green or blue thermosetting coloring compositions, green pixel patterns and blue pixel patterns are sequentially formed on the same substrate as described above. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above order.

In addition, the partition wall not only functions as a light shield, but also functions to prevent color mixing of the thermosetting coloring compositions discharged into the partition area, so the film thickness is thicker than the black matrix used in the first method. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

The method and conditions of the substrate, the radiation light source, and the pre-baking and post-baking used in the formation of the color curing film are the same as the above-mentioned first method. In this way, the film thickness of the pixels formed by the inkjet method is about the same as the height of the partition walls.

On the pixel pattern thus obtained, after forming a protective film as needed, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer can be further formed to make a color filter. The spacer is usually formed using a radiation-sensitive composition, and a spacer (black spacer) having light-shielding properties can also be formed. At this time, a coloring radiation-sensitive composition in which a black colorant is dispersed is used.

The color filter containing the colored hardened film of the present invention formed in this way can balance heat resistance, solvent resistance, and developability at a high level. Therefore, for color liquid crystal display elements, color phototube elements, and color sensors , Organic EL display elements, electronic paper, solid-state photography elements, etc. are extremely useful.

Color filter

The color filter of the present invention includes the coloring cured film of the present invention. Specifically, it is sufficient to provide components such as color pixels, a black matrix, and a black spacer used in the color curing film of the present invention as a color filter.

Display element

The display device of the present invention includes the color-cured film of the present invention. Examples of display elements include color liquid crystal display elements, organic EL display elements, and electronic paper.

The color liquid crystal display element provided with the color curing film of the present invention may be a transmissive type or a reflective type, and an appropriate structure may be adopted. For example, a structure may be adopted in which a color filter is formed on a substrate different from a driving substrate provided with a thin-film transistor (TFT), and the driving substrate and the substrate formed with the color filter are opposed to each other via a liquid crystal layer; In addition, a structure in which a color filter is formed on the surface of a driving substrate provided with a thin-film transistor (TFT) and a substrate formed with an ITO (tin-doped indium oxide) electrode can also be adopted Opposite the liquid crystal layer. The latter structure can significantly improve the aperture ratio, and has the advantage that a bright and high-definition liquid crystal display element can be obtained. Furthermore, in the case of the latter structure, the black matrix and the black spacer may be formed on either side of the substrate on which the color filter is formed and the substrate on which the ITO electrode is formed.

The color liquid crystal display device provided with the color curing film of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp). As the white LED, for example, a combination of red LED, green LED, and blue LED can be used to obtain white light by mixing colors White LEDs, combining blue LEDs, red LEDs, and green phosphors to obtain white light by mixing colors, combining blue LEDs, red light-emitting phosphors, and green emitting phosphors to obtain white light by mixing colors White LED, white LED is obtained by mixing color of blue LED and YAG phosphor, combining blue LED, orange light-emitting phosphor and green light-emitting phosphor to obtain white LED by mixing color It is a white LED that combines ultraviolet light, red light-emitting phosphor, green light-emitting phosphor, and blue light-emitting phosphor to obtain white light by mixing colors.

The color liquid crystal display device provided with the coloring hardened film of the present invention can be applied to a TN (Twisted Nematic, Twisted Nematic) type, STN (Super Twisted Nematic, Super Twisted Nematic) type, or IPS (In-Planes Switching) type. , VA (Vertical Alignment, vertical alignment) type, OCB (Optically Compensated Birefringence, optical compensation curved alignment) type and other suitable liquid crystal modes.

In addition, the organic EL display element provided with the color curing film of the present invention may adopt an appropriate structure, and for example, the structure disclosed in Japanese Patent Laid-Open No. 11-307242 may be mentioned.

In addition, the electronic paper provided with the coloring cured film of the present invention may adopt an appropriate structure, and for example, the structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169 can be cited.

Solid-state imaging element

The solid-state imaging element of the present invention includes the coloring cured film of the present invention. In addition, the solid-state imaging element of the present invention can adopt an appropriate structure. For example, as an embodiment, using the coloring composition of the present invention, it is formed on a semiconductor substrate such as a CMOS substrate by the same operation as described above By coloring pixels (coloring a cured film), a solid-state imaging element with particularly excellent color separation can be produced.

[Example 1]

Hereinafter, examples will be given to further specifically explain the embodiments of the present invention. However, the present invention is not limited to the following embodiments.

<synthesis of colorant> Colorant Synthesis Example 1 Synthesis of dye monomer

Into a 1 L three-necked flask with a stirring bar and nitrogen substitution in advance, add 3.36 g (3.67 mmol) of ginseng (dibenzylacetone)-dipalladium (0), (±)-2,2'-bis(two Phenylphosphino)-1,1'-binaphthalene 4.58g (7.36mmol), and 450mL of 1,2-dimethoxyethane pre-bubbled with nitrogen and degassed, stirred at 80°C under nitrogen flow 1 hour. After that, the mixture was cooled to below 40°C, and without introducing air into the system, sodium tert-butoxide 25.0g (0.260mol), 4-aminocyclohexanol 23.0g (0.200mol), 1- Bromonaphthalene 38.0 g (0.184 mol) was stirred under reflux for 3 hours. Thereafter, after the reaction mixture was cooled to room temperature, it was filtered through celite. In addition, the filtered diatomaceous earth was washed with ethyl acetate. The filtered filtrate of diatomaceous earth and the washing solution for washing the diatomaceous earth with ethyl acetate were mixed, and concentrated under reduced pressure with a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 33.0 g (0.137 mol, yield 74%) of viscous solid. Let this compound be (A1).

Into a 500 mL three-necked flask placed with a stirring bar and performing nitrogen replacement in advance, 12.0 g (0.0497 mol) of the above compound (A1), 7.55 g (0.0746 mol) of triethylamine, and 6.07 g of 4-dimethylaminopyridine (0.0497mol), 250 mL of ethyl acetate, and the internal temperature was cooled to 5°C. After 6.24 g (0.0259 mol) of methacryloyl chloride was added dropwise to the mixture so that the internal temperature did not exceed 10° C., the internal temperature was raised to room temperature, and the mixture was stirred at the same temperature for 4 hours under a nitrogen stream. Thereafter, the reaction mixture was washed with 300 mL of water and 300 mL of saturated brine in this order, and the organic layer was dried over anhydrous sodium sulfate, and then concentrated under reduced pressure with a rotary evaporator until 40 g. Thereafter, 200 g of toluene was added and concentrated under reduced pressure until 40 g with a rotary evaporator, and 85 g of toluene was added again. At room temperature, to the resulting solution were added 4,4'-bis (diethylamino) benzophenone 20.5g (0.0633mol), 4-methoxyphenol 0.100g, phosphine chloride 8.05g (0.0518mol), stirred at 100°C for 2 hours under nitrogen flow. Thereafter, the reaction mixture was cooled to room temperature, and most of toluene was distilled off under reduced pressure with a rotary evaporator. The obtained residue was dissolved in 500 mL of chloroform, and washed with 500 mL of water. The organic layer was concentrated under reduced pressure with a rotary evaporator, and acetone was added to the obtained residue to make the total mass 400 g. Again, the resulting solution was added dropwise to 3200 g of diisopropyl ether, and the resulting solid was filtered off. The solid was dried under reduced pressure at 50° C. for 12 hours to obtain 18.0 g (0.0276 mol, yield 56%) of a colored solid. Let this compound be (A2).

In a 100 mL Erlenmeyer flask containing a stirrer, 9.00 g (13.8 mmol) of the above compound (A2) and 5.94 g (20.7 mmol) of lithium bis(trifluoromethanesulfonyl)imide were added, and 90 mL of ethyl acetate and ions were added Exchange 90 mL of water and stir at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed three times with 100 mL of ion-exchanged water. After the organic layer was concentrated under reduced pressure, the residue was dried under reduced pressure at 50° C. for 12 hours, thereby obtaining 11.4 g (12.7 mmol, 92% yield) of the compound represented by the following formula (A3). Let this be a compound (A3).

Synthesis of dye polymers

A 100 mL three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was replaced with nitrogen. After sufficient nitrogen substitution, 15.0 g of cyclohexanone was placed and heated to an internal temperature of 70±2°C under a nitrogen flow. For this, 9.0 g (10.0 mmol) of the mixed compound (A3), 1.0 g (11.6 mmol) of methacrylic acid, and methyl methacrylate 5.0 were added dropwise for 2 hours using a pump while maintaining the internal temperature of 70±2°C. g (50.0 mmol), 2,2'-azobis(2,4-dimethylvaleronitrile) (produced by Wako Pure Chemical Industries, trade name V-65) 2.02 g (8.13 mmol), ring A solution prepared from 45.0 g of hexanone. After the dropwise addition, stirring was continued at the same temperature for 1 hour. After that, a solution of 0.728 g (2.71 mmol) of 2,2′-azobis(2,4-dimethylvaleronitrile) dissolved in 1.16 g of cyclohexanone was added to the reaction mixture at the same time. Stir at temperature for 3 hours. The reaction solution was cooled to room temperature, and added dropwise to a large amount of hexane. The obtained colored solid was dried under reduced pressure at 50°C to obtain 14.4 g (96% yield) of copolymer. The Mw of the obtained copolymer was 5,300. This polymer is used as a coloring agent (A-1).

Colorant Synthesis Examples 2~3

In "Synthesis of Dye Multimer" in Colorant Synthesis Example 1, the type and amount of monomers used were changed as shown in Table 1, except that the polymer (A- 2)~(A-3). The obtained copolymers were used as colorants (A-2) to (A-3), respectively.

<Synthesis of Adhesive Resin> Adhesive resin synthesis example 1

In a flask equipped with a condenser and a stirring device, 29 parts by mass of propylene glycol monomethyl ether acetate was put in for nitrogen replacement. It was heated to 80°C, and at the same temperature, 30.85 parts by mass of propylene glycol monomethyl ether acetate, 6.06 parts by mass (70.4 mmol) of methacrylic acid, 16.67 parts by mass (166.5 mmol) of methyl methacrylate, A mixed solution of 15.15 parts by mass (93.4 mmol) of phenyl methacrylate and 2.27 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours for polymerization. Thereafter, the temperature of the reaction solution was increased to 100° C., and polymerization was carried out for another hour, thereby obtaining a solution (solid content concentration of 40% by mass) containing the binder resin (B1). Let this be "adhesive resin (B1) solution". The Mw of the obtained adhesive resin (B1) was 9700, and Mn was 4800.

Adhesive resin synthesis example 2~21

Except changing the raw materials used according to Table 2, it carried out similarly to the adhesive resin synthesis example 1, and obtained each adhesive resin solution (solid content concentration 40 mass %). Use these resin solutions as "adhesive resin (B2) solution" ~ "adhesive resin (B21) solution". Adhesive resin (B1)~(B10), adhesive resin (B12)~(B16) and adhesive resin (B18)~(B20) belong to specific copolymers, adhesive resin (B11), adhesive resin (B17) And adhesive resin (B21) is not a specific copolymer. In addition, in Table 2, the "acetal protector of 4-hydroxyphenyl methacrylate" used the compound synthesized by the method mentioned later. In addition, Table 2 indicates the raw materials used in mmol units.

<Synthesis of acetal protector of 4-hydroxyphenyl methacrylate> Synthesis Example 1

In a 2-necked flask with a stirring bar, 150 mL of dichloromethane, 10 g (56.1 mmol) of 4-hydroxyphenyl methacrylate, and 1.41 g (5.61 mmol) of pyridinium p-toluenesulfonate were added, and the mixture was stirred at room temperature. 6.07 g (84.2 mmol) of ethyl vinyl ether was added dropwise over 15 minutes. After the dropwise addition was completed, the mixture was further stirred at room temperature for 3 hours to perform a sufficient reaction. After the reaction was completed, it was extracted with diethyl ether, washed with 1M aqueous sodium hydroxide solution, and then dried over magnesium sulfate. After the solvent was removed, the obtained white solid was purified with a silica gel column to obtain 11.2 g (44.9 mmol, 80% yield) of an acetal protector of 4-hydroxyphenyl methacrylate.

<Preparation of colorant solution> Preparation Example 1

10 parts by mass of the color former (A-1) obtained above was dissolved in 90 parts by mass of propylene glycol monomethyl ether as a colorant solution (A-1).

Preparation Example 2~9

In Preparation Example 1, the types and amounts of colorants and solvents used were changed as shown in Table 3 to obtain colorant solutions (A-2) to (A-9). In addition, in Table 3, "dimethylenepyrrole dye 1" is an exemplary compound III-1 described in JP54 of Japanese Patent No. 5085256, and "PGME" means propylene glycol monomethyl ether.

Preparation Example 10

15 parts by mass of CI Pigment Blue 15 as a coloring agent: 6, 12.5 parts by mass (solid content concentration 40% by mass) of BYK-LPN21116 (made by BYK-Chemie (BYK)) as a dispersant, 0.5 parts by mass CI solvent blue 70 as an additive, 12.5 parts by mass (solid content concentration 40% by mass) of a binder resin (B2) solution, and 59.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent were processed by a bead mill to prepare Pigment dispersion (A-10).

Preparation Examples 11-17

In Preparation Example 10, the types of pigments and adhesive resin solutions used were changed as shown in Table 4 to obtain pigment dispersions (A-11) to (A-17).

<Preparation and evaluation of coloring composition> Example 1

33.0 parts by mass of the coloring agent solution (A-1) as the (A) colorant, and 11.9 parts by mass (solid content concentration of 40% by mass) of the adhesive resin (B1) solution as the (B) adhesive resin (C ) 7.2 parts by mass of a polymerizable compound of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA), NCI-930 as a photopolymerization initiator (ADEKA stock limited (Made by the company) 0.6 parts by mass, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole 0.3 parts by mass, 2,4- 0.2 parts by mass of diethylthioxanthone and 0.2 parts by mass of 2-mercaptobenzothiazole, 0.03 parts by mass of Megafac F-554 (made by DIC Corporation) as a fluorine-based surfactant, and propylene glycol monomethyl ether as a solvent 29.9 parts by mass of acetate and 16.7 parts by mass of diacetone alcohol were mixed to prepare a blue colored composition (BS-1).

Evaluation of heat resistance

After applying a coloring composition (BS-1) on a soda lime glass substrate with a SiO ₂ film on the surface of which prevents sodium ion elution from being formed using a spin coater, it was prebaked on a hot plate at 90°C for 2 minutes to form a film thickness of 2.5 μm coating.

Next, after cooling the substrate to room temperature, the coating film was exposed to radiation at a wavelength of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp through a photomask at an exposure amount of 400 J/m ² . Then, a developer composed of a 0.04% by mass sodium hydroxide aqueous solution at 23° C. was sprayed onto these substrates at a development pressure of 1 kgf/cm ² (nozzle diameter 1 mm), thereby performing shower development for 60 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230° C. for 20 minutes, thereby forming a colored hardened film on the substrate.

With respect to the obtained color-hardened film, the chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system were measured with a C light source and a 2-degree field of view using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.).

Next, the above substrate was additionally baked at 230° C. twice for 20 minutes. The chromaticity coordinate values (x, y) and stimulus values (Y) of the substrate after the two additional baking were measured, and the color change before and after the two additional baking, that is, ΔE ^* _ab was evaluated. As a result, when the value of △E ^* _ab is 1.0 or less, it is evaluated as "◎", when it is greater than 1.0 and 2.0 or less, it is evaluated as "○", when it is greater than 2.0 and 3.0 or less, it is evaluated as "△", and when it is greater than 3.0, it is evaluated as "×"". Furthermore, it can be said that the smaller the ΔE ^* _ab value, the better the heat resistance.

Evaluation of solvent resistance

After applying a coloring composition (BS-1) on a soda lime glass substrate with a SiO ₂ film on the surface of which prevents sodium ion elution from being formed using a spin coater, it was prebaked on a hot plate at 90°C for 2 minutes to form a film thickness of 2.5 μm coating.

Next, after cooling the substrate to room temperature, using a high-pressure mercury lamp, each coating film was exposed to radiation having a wavelength of 365 nm, 405 nm, and 436 nm through a photomask at an exposure amount of 400 J/m ² . Then, a developer composed of a 0.04% by mass sodium hydroxide aqueous solution at 23° C. was sprayed onto these substrates at a development pressure of 1 kgf/cm ² (nozzle diameter 1 mm), thereby performing shower development for 60 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and post-baked in a clean oven at 230°C for 20 minutes, thereby forming a rectangular pattern on the substrate. Thereafter, the above substrate was immersed in a mixed solution of 80° C. mixed with N-methylpyrrolidone:butyl cellosolve=50:50 (volume ratio) for 5 minutes.

The color coordinate values (x, y) and stimulus values (Y) before and after immersion were measured, respectively, and the color change before and after immersion, that is, ΔE ^* _ab was evaluated. When the value of ΔE ^* _ab is 1.0 or less, it is evaluated as “◎”, when it is greater than 1.0 and 2.0 or less, it is evaluated as “○”, when it is greater than 2.0 and 3.0 or less, it is evaluated as “△”, and when it is greater than 3.0, it is evaluated as “×”. Furthermore, it can be said that the smaller the ΔE ^* _ab value, the better the solvent resistance.

Evaluation of developability

After applying a coloring composition (BS-1) on a soda lime glass substrate with a SiO ₂ film on the surface of which prevents sodium ion elution from being formed using a spin coater, it was prebaked on a hot plate at 90°C for 2 minutes to form a film thickness of 2.5 μm coating.

Next, after cooling the substrate to room temperature, using a high-pressure mercury lamp, each coating film was exposed to radiation having a wavelength of 365 nm, 405 nm, and 436 nm through a photomask at an exposure amount of 400 J/m ² . Then, a developer composed of a 0.04% by mass sodium hydroxide aqueous solution at 23° C. was sprayed onto these substrates at a development pressure of 1 kgf/cm ² (nozzle diameter 1 mm), thereby performing spray development. At this time, the time (BP) until the film of the unexposed portion disappeared and the substrate surface was exposed was evaluated. When the BP is within 30 seconds, it is evaluated as "◎", when it exceeds 30 seconds and within 40 seconds, it is evaluated as "○", when it exceeds 40 seconds and within 50 seconds, it is evaluated as "△", and when it exceeds 50 seconds, it is evaluated as "×".

Examples 2 to 21 and Comparative Examples 1 to 3

In Example 1, except for changing the types of the coloring agent solution and the adhesive resin solution used as shown in Tables 5 and 6, the blue coloring composition (BS-2) was prepared in the same manner as in Example 1 ) To (BS-24), evaluated in the same manner as in Example 1. The evaluation results of Examples 2 to 10 are shown in Table 5, and the evaluation results of Examples 11 to 21 and Comparative Examples 1 to 3 are shown in Table 6.

In Tables 5 and 6, each component is as follows.

C-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)

D-1: NCI-930 (made by ADEKA Corporation)

D-2: 2,2’-bis(2-chlorophenyl)-4,5,4’,5’-tetraphenyl-1,2’-biimidazole

D-3: 2,4-Diethylthioxanthone

D-4: 2-mercaptobenzothiazole

F-1: Megafac F-554 (made by DIC Corporation)

E-1: Propylene glycol monomethyl ether acetate

E-2: Diacetone alcohol

E-3: Cyclohexanone

Example 22

27.2 parts by mass of the coloring agent solution (A-2) as the colorant (A), 6.1 parts by mass of the pigment dispersion liquid (A-13), and 10.6 parts by mass of the binder resin (B2) solution (solid content concentration 40% by mass) , (C) a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as a polymerizable compound (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) 6.8 parts by mass, as a photopolymerization initiator NCI-930 ( (ADEKA Corporation) 0.6 parts by mass, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole 0.3 parts by mass, 2 , 0.2 parts by mass of 4-diethylthioxanthone and 0.2 parts by mass of 2-mercaptobenzothiazole, 0.03 parts by mass of Megafac F-554 (made by DIC Corporation) as a fluorine-based surfactant, and propylene glycol as a solvent Monomethyl ether acetate 31.4 parts by mass and 16.7 parts by mass of diacetone alcohol were mixed to prepare a blue colored composition (BS-25).

Using the prepared coloring composition (BS-25), evaluation was performed in the same manner as in Example 1. The results are shown in Table 7.

Examples 23 to 25 and Comparative Examples 4 to 6

In Example 22, the types of colorant solution, pigment dispersion, and adhesive resin solution used were changed as shown in Table 7, except that the blue coloring composition (BS -26) to (BS-31), evaluated in the same manner as in Example 1. Table 7 shows the evaluation results.

In Table 7, each component is as follows.

C-1: Dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate Ester mixture (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)

D-1: NCI-930 (made by ADEKA Corporation)

D-2: 2,2’-bis(2-chlorophenyl)-4,5,4’,5’-tetraphenyl-1,2’-biimidazole

D-3: 2,4-Diethylthioxanthone

D-4: 2-mercaptobenzothiazole

F-1: Megafac F-554 (made by DIC Corporation)

E-1: Propylene glycol monomethyl ether acetate

E-2: Diacetone alcohol

E-3: Cyclohexanone

Example 26

18.7 parts by mass of the pigment dispersion liquid (A-10) as the colorant (A) and 9.9 parts by mass of the colorant solution (A-5), and 14.1 parts by mass of the binder resin (B2) solution as the (B) binder resin (Solid content concentration 40% by mass), 7.0 parts by mass of a mixture of (C) polymerizable compound of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA), as light 0.5 parts by mass of NCI-930 (made by ADEKA Co., Ltd.) as a polymerization initiator, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2' -0.04 parts by mass of biimidazole, 0.02 parts by mass of 2,4-diethylthioxanthone and 0.02 parts by mass of 2-mercaptobenzothiazole, Megafac F-554 (made by DIC Corporation) 0.03 as a fluorine-based surfactant 35.8 parts by mass of propylene glycol monomethyl ether acetate as a solvent and 16.7 parts by mass of diacetone alcohol were mixed to prepare a blue coloring composition (BS-32).

Using the prepared coloring composition (BS-32), evaluation was performed in the same manner as in Example 1. The results are shown in Table 8.

Examples 27 to 31 and Comparative Examples 7 to 11

In Example 26, the type and amount of each component used were changed as shown in Table 8 to prepare a colored composition. Next, using the prepared coloring composition, evaluation was performed in the same manner as in Example 1. Table 8 shows the evaluation results. Furthermore, the coloring composition (BS-32)~(BS-36) is a blue composition, the coloring composition (RS-1)~(RS-4) is a red composition, and the coloring composition (GS- 1)~(GS-2) is a green composition.

In Table 8, each component is as follows.

C-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)

D-1: NCI-930 (made by ADEKA Corporation)

D-2: 2,2’-bis(2-chlorophenyl)-4,5,4’,5’-tetraphenyl-1,2’-biimidazole

D-3: 2,4-Diethylthioxanthone

D-4: 2-mercaptobenzothiazole

F-1: Megafac F-554 (made by DIC Corporation)

E-1: Propylene glycol monomethyl ether acetate

E-2: Diacetone alcohol

E-3: Cyclohexanone

Claims (10)

A coloring composition, comprising: (A) a colorant comprising at least one selected from the group consisting of dyes and dye polymers, the dye polymers having dyes having dye residues and ethylenically unsaturated groups The monomer as a structural unit, (B) an adhesive resin, and (C) a polymerizable compound, as (B) an adhesive resin, a copolymerization ratio containing an ethylenically unsaturated monomer represented by the following formula (1) is 11 A copolymer with a molar content of more than %, wherein the copolymer does not include the dye polymer,

In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkanediyl group having 2 to 4 carbon atoms, R ³ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted polycyclic aromatic group A hydrocarbon group, or a substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group, n represents an integer of 0 to 100, wherein when n is 2 or more, a plurality of R ² may be the same or different. The coloring composition according to claim 1, wherein, in the copolymer, the copolymerization ratio of the ethylenically unsaturated monomer represented by formula (1) is 22 mole% or more. The coloring composition according to claim 1, which contains a dye or a dye multimer selected from triarylmethane dyes as dyes,

Dyes, dimethylenepyrrole dyes and cyanine dyes, the dye polymers are provided with dyes selected from triarylmethane,

Dye monomers of the dye residues and ethylenically unsaturated groups in the dyes of the system dyes, the dimethylpyrrole dyes, and the cyanine dyes serve as structural units. As in the coloring composition of claim 1, wherein n=0 in the formula (1). The coloring composition of claim 1, wherein in the copolymer, the copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) is 60 mol% or less. The coloring composition of claim 1, wherein the dye monomer is a monomer represented by the following formula (2),

In formula (2), R ¹¹ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond, a substituted or unsubstituted divalent hydrocarbon group, or the divalent hydrocarbon group and one or more atoms containing atoms other than carbon atoms and hydrogen atoms The divalent group formed by combining the linking groups of, D ¹ represents a dye residue. A coloring hardened film formed using the coloring composition according to any one of claims 1 to 6. A color filter provided with a color-hardened film as in claim 7. A display element provided with a color-cured film as in claim 7. A solid-state photographic element having a color-cured film as in claim 7.